N-benzothiazol-2-yl-n{40 -propylureas

ABSTRACT

The invention comprises compounds of the general formula   IN WHICH Y1, Y2, Y3, Y4, Y5, R1 and R2 have the meanings given below, their process of manufacture, their use as active ingredients in microbiocidal agents and their methods of use.

United States Patent 1 1 Y J aniak 1 1 Apr.3,1973

N-BENZOTHIAZOL-Z-YL-N PROPYLUREAS I Stefan Janiak, Basel, SwitzerlandAssignee: Ciba-Geigy AG, Basel, Switzerland Filed: Oct. 22, 1969 Appl.No.: 868,589

Inventor:

Foreign Application Priority Data Nov. 1, 1968 Switzerland ..l6333/68US. Cl ..260/305, 424/270 Int. Cl. ..'.....C07d 91/46 Field of Search..260/305 References Cited UNITED STATES PATENTS 7/1956 Searle .260 30512/1970 Zakaria ..260/305 OTHER PUBLICATIONS Fujikawa et al., Chem.Abstracts, 70:77857n (1969). Joshua, Chem. Abstracts, 55:8389 (1961).

Moore, Chem. Abstracts, 67:64387x (1967-). Winner et al., Chem.Abstracts, 68:113546e (1968).

Primary ExaminerAlex Mazel Assistant ExaminerR. J. GallagherAttorneyHarry Goldsmith, Joseph G. Kolodnyand Mario A. Monaco p [57]ABSTRACT their use as active ingredients in mierobiocidal agents andtheir methods of use.

-3 Claims, No Drawings N-BENZOTHIAZOL-Z-YL-N-PROPYLUREAS The presentinvention provides rriicrobiocidal agents which comprise, as the activeingredient, a compound of general formula Y1 v f R Y2 1 Met-..

in which Y Y Y and Y, each represent a hydrogen or halogen atom, analkyl, alkoxy, alkylthio, carboxyl,

,carboxyalkyl, nitrile, .thiocyanato, nitro, sulphonic acid, sulphonicacid amide, monoalkylsulphonic acid amide, dialkylsulphonic acid amideor optionally substituted'phenyl residue, R represents a hydrogen atomor an alkyl residue, R represents the group OR NHR or -N(R )(R Rrepresents an alkyl, alkenyl, alkinyl or optionally substitutedphenylresidue, R represents a hydrogen atom or an alkylresidue, R representsan alkyl, cycloalkyl, alkenyl, alkinyl, alkoxy or-optionally substitutedphenyl residue and R and R together with the N-atom to which they arelinked form a 3-membered to 7-membered heterocyclic ring, with theproviso that if R, represents a methyl residue, one

of the substituents, Y Y Y and Y, is other than a hydrogen atom,optionally together with a liquid or solid carrier or other additive.

The alkyl, alkenyl, alkinyl, alkoxy or alkylthio residues which Y to Y RR R and K, may represent, contain one to 18 or two 'to 18 (in the caseof the alkenyl or alkinyl residues), but preferably one to four or twoto four carbon atoms. These residues may be branched or straight-chain,unsubstituted or substituted. The cycloalkyls preferably contain threeto six carbon atoms in the ring.

As halogen atoms there may be mentioned F, Cl, Br and I atoms. PossibleC alkyl, C alkenyl andC alkinyl residues are preferably, for-example,methyl, trifluoromethyl, ethyl, propyl, isopropyl, ni-, sec.- ortert.-butyl, allyl, methylallyl, chlorallyl, methylpropenyl, propinyl oriso-butinyl residues.

Thesubstituents on the alkyl, alkenyl, alkinyl, alkylene, alkoxy,alkylthio and phenyl residues may be of the first order or of the secondorder. By substituents of the first order there are here to beunderstood electron donors which increase the basicity. Here possiblegroups are, amongst others: halogen atoms such as fluorine, chlorine,bromine or iodine atoms, alkoxy and alkylthio groups with one to fourcarbon atoms which may be branched or unbranched, but preferably areunrepresents F or Cl, lower alkylsulphinyl' groups and loweralkylsulphonyl groups which possess a branched or unbranched alkylresidue with one to four carbon atoms, preferably an unbranched alkylresidue with one. or two carbon atoms.

Compounds'of especial importance are those of forin formulas II to VI Yrepresents a number, defined by n, of identical or different halogenatoms, C alkyl,

C alkoxy, C alkylthio, carboxy C alkyl or nitro groups, n is an integerof 1 to 4, R representsa C alkyl, C alkenyl or optionally substitutedphenyl residue, R and R each represerits'a C alkyl residue or a3-membered to 6-membered cycloalkyl residue, R

represents a C alkyl residue or an optionally substituted phenylresidue. i

As examples of suitable compounds of formulas l to VI, the following maybe quoted:

The present invention also provides the phenylureas of formulas I to VI.They may be manufactured according to methods which are in themselvesknown, for example by reaction of an aromatic residue with a secondreagent B, so that Y to Y have the meanings given for formula I, whilstone of the sub-v stituents A or B represents an amine component in whichone or both free valencies are bonded to H, to the extent that theyare'not constituents of a primary or secondary amine, whilst the otherrepresents the grouping wherein R can be an easily removable residuewhich contains C or A represents NH or -NHR and B represent the groupingClCOOR wherein R has the 7 meaning given for formula l.

The compounds of formula I can preferably be manufactured: a. Byreaction of an aromatic residue with a primary or secondary amine offormulas /Rl HQN HNR5 which both together can form the urea grouping, so

that therein Y to Y R and R have the meanings given for formula I,whilst A represents the grouping 1] l i TIM -N-COORV, -NCO halogen,NCONH2 or N C O, R" alkyl or aryl, and R, has the meaning given forformula I.

b. By reaction of an amine of formula with one of the compounds offormulas NCOOR R R N e C o,'R 'aryl. Herein Y, to Y,,-R,- and R, havethe meanings given-for formula I.

c. By reaction of an amine of formula with a compound of formula ple,Erysiphe cichoracearum DC., Alternaria vtenius or solani, Uromycesphaseoli Pers. Piricularia oryzae Bri. et Cav. and Botrytis cinereaPets. The invention relates to the use of the compounds of formula I asactive ingredients in microbiocidal preparations. I

The preparations according to the invention contain, in addition to theactive ingredient of formula I, a suitable carrier and/or otheradditives. Suitable carriers and additives can be solid or liquid andcorrespond to the substances which are usual in formulation technologysuch as, for example, natural or regenerated mineral substances,solvents, diluents, dispersing agents, emulsifiers, wetting agents,adhesives, thickeners, binders or fertilizers. Furthermore, yet furtherbiocidal compounds can be added. Such biocidal compounds can, forexample, belong to the class of the ureas, the saturated or unsaturatedhalogenobenaonitriles, halogenobenzoic acids, phenoxyalkylcarboxylicacids, carbamates, triazines, nitroalkylphenols, organic phosphoric acidcompounds, quaternary ammonium 3 diesel oil or kerosene, coal tar oilsand oils of vegetable or animal origin, as well as hydrocarbons such asalkylated naphthalenes, tetrahydronaphthalene, xylenes,

cyclohexanol, ketone and also chlorinated hydrocarbons such as.trichlorethane land tetrachlorethane, trichlorethylene ortriehlorobenzenes and tetrachlorobenzenes, individually or in mutualcombination. Solvents of which the boiling point lies abov 100 C areadvantageously used.

. 6 improve the distribution, adhesion, 'rain resistance orpenetratingpower; as such substances there may be mentioned: fattyacids, resins, glue, casein or alginates.

In many cases the use of granules for the uniform release of activesubstances over a longer period of time is of advantage. These granulescan be manufactured bydissolving the active substance in an organicsolvent, absorbing this solution by means of a granular material, forexample, attapulgite or so, and removing the solvent..They can also bemanufactured by mixing the active substances of formula Iwithpolymerizable compounds, after which a polymerization is carried outwhich leaves the active substances unaffected, with the granulationbeing carried out whilst the polymerization is still proceeding. Thecontent of active substance in the agents described above is between0.01 and 95 percent and itshould be mentioned in this context that onapplication from aircraft or by means of other suitable applicationequipment concentrations of up to 99.5 percent or even pure activesubstance are employed. The following Examples illustrate the invention:

EXAMPLE 1 I Manufacture of the compound of formula -NH.CO-NH-CH;Compound N0. IV

' 58.2 g (0.3 mol) of 2-amino-fiethoxybenithiazole Aqueous applicationforms are especially appropriately prepared from emulsionconcentrates,pastes or wettable spraying powders by adding water.

'Possible emulsifiers or dispersing agents are non-ionic products, forexample, condensation products of aliphatic alcohols, amines orcarboxylic acids having a long-chain' hydrocarbon residue of about l0 tocarbon atoms with ethylene oxide, such as the condensation product-of'oct adecylalcoh ol and to mols of ethylene oxide, or that of soya fattyacid and 30 mols of ethylene oxideor that of technical oleylamine and 15mols of ethyleneoxide or that of'dodecylmercaptan and 12 mols ofethylene oxide. Amongst the anionic emulsifiers which can be employedthere .may be mentioned:' the sodium salt of 'dode'cyl alcohol sulphuricacid ester, the sodium salt of dodecylbenzenesulphonic acid, thepotassium or triethanolamine salt of oleic acid or of abietic acid or ofmixturesof these acids or the sodium salt of a petroleum, sulphonicacid. Possible cationic dispersing agents are. quaternary ammonium aresuspended in 450 ml of dry benzene and heated to 80 C, whereupon thesubstance dissolves. 20 ml of methylisocyanate are added dropwise atthis temperature. After about 12 ml of methylisocyanate have been addeddropwise, a precipitate begins to separate out. Thereafter the mixtureis stirred for a further 2 hours at 80 C and then cooled to 5 C, and theproduct is filtered off. This is-immediately obtained'in an analyti-"cally pure form. Melting point: 222'-224C. Yield: 73 g 97 percent.

I v EXAMPLE 2 Manufacture of the compound of formula Compound N0. 2

60 m l of pyridine are cooled to 5 C and mixeddropwise with 32.5 g ofdimethylcarbamic acid chloride. 58.2 g of 2-amino-6-ethoxybenzthiazoleare added to this mixture, initially kept at 5 C, whilst stirring, withcare having to be taken-that the temperature does not exceed-50 CvThereafter the reaction mixture is kept fo'r -21hours at 50 C. It isthen cooled to room'temperature whilst stirring and mixed-with 500ml ofwater, and the product which has precipitated is filteredoff.Meltingpoint: l' 73l'75 C/Yield: 75 g= 93.5 percent.

' The a following compounds were manufactured analogously:

I R /N\ N11-cI; 11 11' \S Mnltlng point, Compound No. R R ll R 11" (1.

3 .1 11 11 11 1111-17 4 11 11 11 111111111 6 11 11 11 1112-111 11. 11 1111 1111-111 7 11 11 11 1111-1111 11.. 11 11 11 117-11 1 11 11 11 111115-117 111 11 11 11 145-411 11 11 11 (:1 1113-1111 12 11 11 112411-112 13 11 11 11 1711-111 1 1 11 11 21111 111 11 ()(3ll 1 a011 11111 o11 1211-24 17 11 11 2111-3 111 11 11 11 243 47 111 11 11 (:1 2711211 11 11 4102115 21111-2112 211 11 11 111 2411-511 22 11 11 11 *2111523 11 11 -1111.-, 257

ll 11 11 -0C111, 11 256- H 11 -00111 11 2117-2111; 11 11 01 1-1 270 1111 -OC2H1 11 222-24 11 11 .c111 270- -c111 11 -N01 2011-12 30 1.NHr1(C;H 0( 11115 11 11 0C1H5 156-58 11 NH-n(C1H H 11 001115 11 181-83-NH11(C;H1) --00H@ 11 11. c11;1 171-73 NH-n(O;H -oc111 11 11 -85NH11(G;H OCH;1 11 II 01 -68 NH-11(C; 1) 11 11 0c111 11 163-65 NH11(C;H1)c1 11 11 11 1118-1111 -NH11(C;H1) 0c,111 11 11 11 1611-71 NH-n(c1111) 1111 -0C111 11 166-67 -NHi(C;1H 11 11 -0c,111 11 -84 N(CH;1)2 11 11 ()CII111 210-215 011111 11 11 SCII1 11 1115-107 N(CH;)1 11 11 (11 11 *2111 N0111)2 11 11 0111 11. 1111 N(Cll; )g 11 11 #1111111, 11 173-75*Doumnpositio11.

EXAMPLE 3 ml of dry.pyridine. 36 g of chloroformic acid ethyl esterManufacture of the compound offormula are added dropwise at roomtemperature. The mixture 45 1s finally stirred overmght, and the orgamcphase is /N washed in a separating funnel with water, sodium bicar- NHC0OC2H5 compound No. '45 bonate'solution and saturated sodium chloridesolution p until neutral, dried over sodium sulphate and evaporated todryness under reduced pressure. Melting 50 point l98200 C (fromalcohol); yield: 62 g =91 per- 45.6 g [0.3 mol] of Z-amino-benzthiazoleare dissolved in 450 ml of dry ethyl acetate and mixed with 24 cent;

The following compounds of general formula are manufactured analogously.

' Fungicidal test Equal parts of an active ingredient of the inventionand precipitated silica are finely ground. Dusting agents preferablycontaining 1 to 6 percent of active ingredient can be manufacturedtherefrom by mixing with kaolin or talc.

Spraying powders In order to manufacture a spraying powder, thefollowing components are, for example, mixed and finely ground: p

- 50 parts of an active ingredient of the present invention r parts ofHlSlL' (highly adsorbent silica) parts of Bolus alba (kaolin)kylphenolwith ethylene oxide and calcium; dodecylbenzenesulphonate aremixed. 'O'nfdilution with water to the desired concentration, a spraya-'ble emulsion is produced.

Granules 7.5 g of one of the active ingredients of formula I aredissolved in l00 ml of acetone and the acetone solution thus obtained'is applied to 92 g of granulated attapulgite (mesh size: 24/48meshes/inch). The whole is well mixed and the solvent is stripped off ina rotational evaporator. A granular material containing 7.5 percent ofactive ingredient is obtained.

EXAMPLES a. Cucumber mildew (Erysiphe cichoracearum 0.0. v

Cucumber plants were grown in agreenhouse and sprayed onceprophylactically with aqueous spraying broths each containing 0.1percent of the test active Table Continued Melting point, Compound No. RR Rf" R' R C.

4s .CH; II 1i 11 11 185-87 -ocr1 40.. 0C"iH9-,, ir ll ll n 158m 50OCH:'CH C-H 11 ll 11 u 1x345 51 011; ll ll ll u 170 A -o-cH2cn 52..O-CH2-CH:-llr ll ll. ll ant-1s 53.. ll ll. ,o 0.415 n 2304;: 54.; ll 1 l"-01 11 25m 55.. ll u l u 210 56 ll u -OU:ll. ll ins-n5 Decomposition.

EXAMPLE 4 cubation in the greenhouse, the treated plants were examinedfor fun al attack. Dusting agents 20 g RESULTS Active Substance No.Fungal Attack way were infected with uredospores of Uromyces phaseoli(Pers.) Wint. and introduced into a humidity chamber for 2 days. After10 to 14 days subsequent incubation in the greenhouse, the treatedplants were examined for fungalattack.

RESULTS Active Substance No. v I: Fungal Attack s I0 The untreatedcontrol plants were 100 percent attacked by fungi.

0. Grey rot (Botrytis cinerea Pers.) Freshly cut vine leaves of theRiesling and Sylvaner variety are sprayed with aqueous broths eachcontaining 0.1 percent of the test active ingredients. Afterdrysubstances. Two days thereafter the plants treated in this way wereinfected with spores of Erysiphe cichoriacearum DC. After 12 to 14 dayssubsequent ining the spray deposit, the leaves are infected with anaqueous conidia suspension of Botrytis cinerea Pers.

and incubated in a humidity dish. After 4 days the treated vine leavesare examined for fungal attack.

I claim: I 1. Compounds of the formula 2 A compound as elaimed in claim1 wherein R represents n-propyl.

3. A compound as claimed in claim 1 wherein R C II O representsisopropyl.

wherein R represents C alkyl.

2. A compound as claimed in claim 1 wherein R9 represents n-propyl.
 3. Acompound as claimed in claim 1 wherein R9 represents isopropyl.